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SUPPORTING INFORMATION

Aromatic Reactivity Revealed: Beyond Resonance Theory & Frontier Orbitals

James J. Brown and Scott L. Cockroft*

EaStCHEM School of Chemistry, University of Edinburgh

King’s Buildings, West Mains Rd, Edinburgh, EH9 3JJ, UK

E-mail: [email protected]

Contents:

Methods

Supporting Figures S1 to S19

Supporting Tables S1 to S3

Supporting References 61 to 328

Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2013

mailto:[email protected]

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Methods Minimised geometries and molecular surfaces were calculated using Spartan ’08 with

DFT/B3LYP/6-311G*, unless otherwise indicated. ionisation energies and electrostatic

potentials are plotted on the 0.002 electrons/bohr3

density surface. Ionisation energy

surfaces emphasising minima are scaled from the average local ionisation energy

minimum on the molecular surface, ĪS,min (red) to ĪS,min +0.4 eV (blue) of each molecule.

A step-by-step guide describing how this was done is provided on the following page.

ĪS meta and ĪS para values for the plots in Figures 3 and S17 were taken on the 0.002

electrons/bohr3 average local ionisation energy surface directly over the centre of the

carbon atoms perpendicular to the plane of the aromatic ring as shown in Figure S1.


S3

Step-by-step guide for calculating ionisation energy surfaces using Spartan ‘08:

1) Open the ‘Model Kit’ structure drawing tool by selecting ‘New’ from the ‘File’ menu,

and draw a structure of interest. Using benzene as an example, click the "Rings" button

and left click in the drawing window.

2) Click the ‘Setup’ menu and select ‘Surfaces’ to open the surfaces window.


S4

3) Click the ‘Add’ button and select ‘ionization’ from the ‘Property’ drop-down menu.

Additionally, electrostatic surfaces can be added by selecting ‘potential’, while the

HOMO and LUMO visualisations are available under the ‘Surface’ drop-down menu.

4) Select ‘Calculations’ from the ‘Setup’ menu in the main program window. In the

window that opens, select ‘Density Functional’ from the ‘with’ menu, then select the

required functional and basis set. In this work, the B3LYP functional was used with the

6-311G* basis set. Click ‘Submit’ to save and start the calculation.


S5

5) After the calculation is complete, open the surfaces window by selecting ‘Surfaces’

from the ‘Setup’ menu, and check the box to the left of the ‘density’ ‘ionization’ entry.

6) To scale the surface appropriately, open the properties window by selecting

‘Properties’ from the Display menu in the main program, and left-click click anywhere on

the surface of the molecule.


S6

7) The surface can be scaled by changing the values in the ‘Property Range’ boxes. The

procedure used in this work leaves the minimum value unchanged and the maximum

value is adjusted to the min+0.4 eV. The surface can be made transparent by selecting

this option from the ‘Style’ drop-down menu. Furthermore, the model can be changed to

‘Ball and Spoke’ via the ‘Model’ menu in the main program window. To read a value

from a specific point on the surface, place the cursor over that point. The value at the

cursor point is shown on the left of the properties window as “Val: 9.787659” eV in this

example.


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Method Selection:

We quickly established that average local ionisation energy calculations performed using

Density Functional Theory (DFT) successfully rank the relative nucleophilicities of

aromatic carbons and heteroatoms where previously used Hartree-Fock (HF) methods

sometimes fail (Figure S2) 25, 61-63

. Indeed, average local ionisation energies calculated

using DFT have been shown to be theoretically robust ,61

and were also employed in the

most detailed assessment of local average ionisation energies prior to the present study

(21 aromatic molecules)20

.

Correlations of average local ionisation energy minima calculated using DFT and various

basis sets against experimental reactivity parameters were also found to be better than

corresponding calculations performed using HF (Figures S16-S17).

Figure S1. Example showing the positions on the 0.002 electrons/bohr3 average local

ionisation energy surface corresponding to ĪS meta and ĪS para in the example of

trifluoromethyl benzene.

ĪS meta

ĪS para


S8

Figure S2. Experimental reactivity patterns for a range of aromatic substrates and

corresponding average local ionisation energy surfaces at the 0.002 electrons/bohr3

surface calculated using the methods shown. Examples where the calculation correctly

ranks the relative nucleophilicities of different reactive sites are highlighted with a green

background. References for the observed reactivity patterns are given in the captions of

other Supporting Figures.


S9


S10

Figure S3 (on preceding page). Comparison of surface-encoded ionisation energy

surfaces, electrostatic potentials, HOMO and HOMO-1 lobes of monosubstituted

benzenes in relation to their experimental reactivity in electrophilic aromatic substitution

reactions. Surface-encoded ionisation energies account for the reactivity of

monosubstituted benzenes and the magnitude of these minima correspond with the

relative nucleophilicities of these molecules. There is no obvious link between purely

electrostatic or orbital-based models and the reactive behaviour of this series of

molecules. The ionisation energy surfaces emphasising the relative reactivity of different

molecules in the second row are plotted on a standardised scale from 8.7 eV (red) to 10.7

eV (blue). Electrostatic potentials are scaled from the lowest potential on each aromatic

ring (red) to this value plus 15 kJ mol-1

(blue). HOMO and HOMO-1 lobes correspond to

0.032 electrons/bohr3. References for the observed reactivity patterns are given in the

captions of the other Supporting Figures.

For a general review of nitration by electrophilic

aromatic substitution64

Phenoxide anion:

Reimer-Tiemann reaction32, 65

Allylation66

Kolbe-Schmitt reaction31

Chlorination29

Benzoate anion

Chlorination38

Bromination39

Anisole

Bromination30,35

Chlorination29, 30, 67

Iodination30, 68, 69

Nitration70

Formylation71

Toluene

Chlorination30, 67, 72-74

Bromination75,30, 35, 74, 76

Iodination30, 36

Nitration70, 77, 78

Trimethylphenyl silane

In Pd-catalysed cross coupling reactions79

Review80

Desilylation (reaction with H+)

81

Bromination82

Chlorination83

Iodination84, 85

Nitration85

Fluorination86

Phenylboronic acid

Nitration87

Chlorobenzene and other halobenzenes

Nitration28, 70, 78

Chlorination29, 30, 67

Bromination 30,35

Iodination36

Phenylacetonitrile

Nitration42, 88

Benzonitrile

Nitration34, 37, 78

Bromination75,35

Chlorination34

Iodination36

Nitrobenzene

Nitration34, 78

Iodination89, 90

91

Bromination30, 75,35

Chlorination30, 34

Benzyltrimethyl phosphonium cation

Nitration92

Trimethylphenyl phosphonium cation

Nitration41, 92

Trimethyl anilinium cation

Nitration41, 93

Anilinium cation

Nitration93, 94


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Figure S4. Experimental reactivity patterns and corresponding calculated average local

ionisation energy surfaces and minimum values (ĪS, min) at the 0.002 electrons/bohr3

surface for cationic monosubstituted benzenes. Calculations were performed using the

LACVP combination of basis sets where DFT/B3LYP/6-311G* was not supported.

References for the observed reactivity patterns are given below.

Anilinium cation

Nitration93, 94

Trimethyl anilinium cation

Nitration41, 93

Trimethylphenyl phosphonium cation

Nitration41, 92

Benzyltrimethyl phosphonium cation

Nitration92

Trimethylphenyl arsonium cation

Nitration41, 92

Trimethylphenyl antimony(V) cation

Nitration92

Triphenyl oxonium cation

Nitration41, 95

Triphenyl sulfonium cation

Nitration96

Dimethylphenyl sulfonium cation

Nitration41

Dimethyl selenonium cation

Nitration41


S12



surface for phenyl derivatives used in metal-catalysed cross-coupling reactions and ipso-

substitution reactions. Calculations were performed using the LACVP combination of

basis sets where DFT/B3LYP/6-311G* was not supported. References for the observed

reactivity patterns are given below.

General:

For excellent general overview of metal-

catalysed cross coupling reactions14, 79

For other more specific literature:

Phenyl lithium

General9

ipso-Fluorination97

Phenyl sodium

General98

Phenyl zinc chloride

ipso-Bromination99

Phenyl mercury(II)chloride


ipso-nitration and nitrosation101

Triphenyl indium

In metal-catalysed cross-coupling reactions102

Trimethylphenyl silane

Review80


S13

Desilylation (reaction with H+)

81

ipso-Bromination82

ipso-Chlorination83

ipso-Iodination84, 85

ipso-Nitration85

ipso-Fluorination86

5-Phenyl-1-aza-5-germabicyclo[3.3.3]undecane

In metal-catalysed cross-coupling reactions79

Trimethylphenyl stannane

ipso-Fluorination86

ipso-Nitration, Nitrosation101


Tetraphenyl plumbane

ipso-Nitration, Nitrosation101

Triphenyl bismuthine

ipso-Nitrosation101


S14



surface for heterocycles used in metal-catalysed cross-coupling reactions. Calculations

were performed using the LACVP combination of basis sets where DFT/B3LYP/6-

311G* was not supported. References for the observed reactivity patterns are given

below.

General For an excellent overviews of metal-catalysed

cross coupling reactions79, 103

2-Furanyl lithium Reaction with carbonyls

104

3-Furanyl lithium Reaction with aldehydes

105 106-109

Reaction with ketones110

2-Thienyl lithium Reaction with esters

111, 112

Reaction with amides113, 114

Reaction with Weinreb amides115

Reaction with carbonyl116

Reaction with Vilsmeier reagent117-119

Reaction with carbon dioxide120


S15

Reaction with carbonates121

2-Thienyl sodium General

98

2,5-Dimethyl, 3-thienyl lithium

With alkenes122

2-Trimethylsilyl, 5-methylthiophene:

ipso-substitution123-126

2-Furanylmagnesium bromide

Reaction oxycarbenium ions 127

2-Thienylmagnesium bromide

Reaction with carbonyls128

129, 130

Reaction with esters131

Reaction with Weinreb amides132

Reaction with alkenes 133, 134

2-Furanyl zinc bromide

Negishi coupling135, 136

2-Pyridylmagnesium chloride

Kumada coupling137

2-Tributylstannyl thiophene:

Stille coupling138, 139

Methyl 1-(N,N-dimethylsulfamoyl)-3,4-

bis(trimethylsilyl)-1H-pyrrole-2-carboxylate

ipso-substitution140

ipso-Iodination during formal total synthesis of

lukianol A141

3-Tributylstannyl 5-methoxybenzofuran

Stille coupling138

(Acetato)(indol-3-yl) mercury

Pd-catalysed cross-coupling142

Tri(2-furanyl) aluminium

Reaction with an epoxide143


S16



surface for multiply-substituted benzenes. References for the observed reactivity patterns

are given below.


S17

p-Nitrotoluene

Bromination144,35

p-Fluorotoluene

Nitration145

p-Methylphenol

Bromination146

1,2,3-Trimethylbenzene

Nitration43

1,2,4-Trimethylbenzene

Nitration43

N,N-diethyl-2-(trimethylsilyl)benzamide

Iodination, bromination, chlorination, ipso-

borodesilylation83

2-(trimethylsilyl)phenyl diethylcarbamate Iodination, bromination, chlorination,

nitrosation, ipso-borodesilylation83

4-nitro-2-(trimethylsilyl)phenyl

diethylcarbamate

Bromination83

N,N-diethyl-2-methoxybenzamide

Nitration83

2-Methoxyphenyl diethylcarbamate

Nitration83

N,N-diethyl-2-methoxy-6-

(trimethylsilyl)benzamide

Nitration83

2-Methoxy-6-(trimethylsilyl)phenyl

diethylcarbamate

Nitration83

3,5-dinitrosalicylic acid

Nitration147


S18



surface for 5-membered heterocyclic rings. References for the observed reactivity

patterns are given below.

For a general review of the substitution of

5-membered rings148

Pyrroles

Nitration77, 149, 150

Nitration: reversal of 2– vs. 3–substitution ratio

upon N–substitution of pyrroles151

Halogenation152, 153

Acetylation: mostly in the 2–position, 3–position

minor product154

Formylation in 2–position71

2- and 3-EDG pyrroles

Note that electron–rich pyrroles tend to be highly

reactive and unstable.

Formylation (EDG = 2–Me)155

2-EWG-pyrroles

Bromination (EWG = NO2)49, 50

Nitration, halogenation and acetylation (EWG =

COCCl3)48

Nitration (EWG = COCH3)51

3-EWG-pyrroles

Alkylation, halogenation (EWG = COPh)156

Acylation (EWG = COPh–p–OMe)157

Formylation (EWG = COOEt)158

Thiophenes


Bromination, chlorination30, 67, 161

Acylation162

Formylation71, 163

Addition at sulfur (hashed arrow)164

2-EDG thiophenes

Bromination, Chlorination (EDG = OMe)5–

position most reactive 165-167

3– and 5–

positions139, 168

Iodination (EDG = Me, OMe, OC=OMe)69, 169

Nitration (EDG = Me)160

Formylation (EDG = OMe) 5–position most

reactive71


S19

2-EWG thiophene

(EWG = NO2, CN and CHO) 5–position most

reactive, 4–position 2nd

most reactive, 3–position

3rd

most reactive159

Chlorination (EWG = Cl, Br)67

Nitration (EWG = Cl)160

Iodination (EWG = Cl, Br, I, CN, NO2, CHO,

COCH3, CO2CH3)69, 169

3-EDG thiophenes

Bromination (EDG = alkyl, OMe)170,167, 171

Iodination (EDG = alkyl)172

3-EWG thiophenes

(EWG = NO2, CN and CHO) 5–position most

reactive, 2–position 2nd

most reactive, 4–position

3rd

most reactive159

Hydroxyalkylation (EWG = Cl)173

Furans

Note that some of the substitution reactions of

furans may not–proceed through a typical

electrophilic aromatic substitution reaction

mechanism, but through an addition–elimination

mechanism, although the position of the initial

attack of the incoming electrophile determines

the regiochemistry of the final product as in a

typical EAS reaction mechanism.

Nitration77, 174

Formylation71

Bromination175

Acetylation176

Oxidation with osmium tetroxide (unfilled

arrow)177

2–EDG furans

Formylation (EDG = alkyl)178

Michael addition (EDG = OMe)179

180

Acylation (EDG = alkyl)181

Chlorination (EDG = t–Bu)152

2–EWG furans

Nitration (EWG = NO2)182, 183

3–EDG furans

Formylation, acylation (EWG = OMe, alkyl)184

185

3–EWG furans

Formylation (EWG = COOMe)186

Oxazole

pKa of conjugate acid = 0.8187

Oxazoles tend to undergo addition rather than

substitution (unfilled arrow)188

Imidazole and cation


Nitration190

Bromination191


arrow)192

Thiazole


Nitration193

Pyrazole and cation


Iodination195, 196

Bromination and Chlorination197

Nitration190, 198

Isothiazole

pKa of conjugate acid = –0.5187

Halogenation199, 200

Nitration200

Isoxazole


Nitration201-203

Bromination204, 205


S20



surface for fused 5-membered heterocycles. References for the observed reactivity


Indole

Formylation71, 206

Mannich reaction207

Halogenation208

Nitration77


arrow)209

Benzofuran


Formylation212

Hydroxyalkylation173

Addition at carbon (unfilled arrow)213

Benzothiophene

Halogenation214-217


Acetylation219

Hydroxyalkylation173

Addition at carbon (unfilled arrow)213

Addition at sulfur (hashed arrow)164

Indolisine

Nitrosylation, formylation220

Acylation221

Nitration222

Imidazo[1,2-a]pyridine and cation


Bromination224

Chlorination224

Acylation225

Nitration224

Imidazo[1,5-a]pyridine and cation


Acylation226

Nitration227

Pyrazolo[1,5-a]pyridine


Formylation, acylation228

N-tert-Bu-BN-Indole

Bromination, Mannich Reaction, Michael

Addition, Deuteriation, Acylation56


S21



surface for biphenyl and naphthalene derivatives. References for the observed reactivity


Carbazole

Bromination229, 230

Alkylation231

Dibenzofuran

Halogenations, Friedel-Crafts and

protodetritiation reactions (note that some

nitration reactions follow a charge-transfer

mechanism to gives the 3-product rather than the

2-product) 52

Iodination232, 233

Alkylation, acylation234

Dibenzothiophene

Halogenation214

Biphenyl

Nitration70, 235-237

Chlorination67

Naphthalene

Nitration70, 235

Halogenation67, 214

Acylation238

Addition & oxidation reactions239

Reaction with ethyl diazoacetate (unfilled

arrow)240


arrow)241

10,9–Borazaronaphthalene

Bromination and deuteration242

1–Methoxynaphthalene

Nitration243

Iodination69

1–Nitronaphthalene



S22

2–Methoxynaphthalene

Nitration243

Bromination246

Iodination68, 69, 247

2–Nitronaphthalene

Nitration248


S23



surface for pyridine derivatives. References for the observed reactivity patterns are given

below.

Pyridine and cation


Halogenation250

Nitration251

252

4–EDG pyridines

Bromination (EDG = OMe, OH, NH2)253

Nitration (EDG = OMe)254

3–EDG pyridines

Bromination (EDG = OMe, OH, NH2)253

2–EDG pyridines

Bromination (EDG = OMe, OH, NH2)253, 255

Chlorination (EDG = NH2)256

Pyridine N–Oxide


Bromination252, 258

Pyridinium N–Oxide cation

Nitration252

Chlorination259

4–Pyridone cation

pKa = 3.3249


Uracil

Phenylsulfenylation262

Bromination263

Iodination264, 265]{#338, 266, 267

Nitration160


S25

Figure S12.Experimental reactivity patterns and corresponding calculated average local


surface for quinoline derivatives. References for the observed reactivity patterns are

given below. Quinoline and cation


Bromination268-271

Chlorination272

Iodination273

Nitration190, 252, 274-276

Fluorination277

Quinoline N–Oxide and cation



Nitration with N2O5281

Isoquinoline and cation



Bromination270, 284, 285

in 5 and 8–positions in

strong acid 271

Isoquinoline N–Oxide


Nitration287

Isoquinolinium N–oxide cation

Nitration280, 288

4–Quinolone (X = NH)


Nitration289

Chromone (X = O)


Bromination291

Mannich reaction292

4–Hydroxyquinolin–1–ium cation (X = NH)

Nitration293-295

4–Hydroxychromenylium cation (X =O)

Nitration296, 297


S26



surface for 7-membered aromatics. References for the observed reactivity patterns are

given below.

Azulene

Iodination68

Tropolone and cation

pKa of conjugate acid of tropolone = –0.9298

Azo–coupling, nitrosation, nitration, sulfonation,

halogenation, hydroxylation,

hydroxymethylation, Reimer–Tiemann

reaction299, 300

Dihydro–1,4–diazepinium cation

pKa = 13.4 (5,7–dimethyl derivative)301

Bromination302-304

Nitration47, 305



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surface for

polycyclic aromatics. Values in parentheses refer to the values taken over regions with double-

bond character as discussed in the main text. References for the observed reactivity patterns are

given below.

Phenanthrene

Nitration235

Halogenation67, 214

Bromination306

Addition & oxidation reactions (unfilled arrow)240, 241,

307, 308

10–Methyl–10,9–Borazarophenanthrene

Bromination and chlorination55


S28

Nitration and chlorination54

Acetylation53

Steric congestion inhibits reaction at carbon 453

10–Hydroxy–10,9–Borazarophenanthrene

Bromination and chlorination55

Nitration and chlorination54

Acetylation53

Benzo(c)phenanthrene

Acylation238

Bromination, nitration, acetylation309

Oxidation with osmium tetroxide (unfilled arrow)310

Chrysene

Nitration235, 311

Halogenation214

Acetylation312

Acylation238, 313

Oxidation with osmium tetroxide (unfilled arrow)310,

314

Triphenylene

Small electrophiles react preferentially in the most

reactive 1–position, while larger electrophile react in

the 2–position due to the steric hindrance in the 1–

position.

1–chlorination and 1–deuteriation315

mostly 1–nitration, some 2–nitration316

311

mostly 2–nitration, some 1–nitration235, 311

2–halogenation214

2-acylation238

Fluoranthene

mostly 3–nitration, some 8–nitration 311

Anthracene

Acylation238

Halogenation67, 214, 306

Nitration317

Addition & Oxidation reactions (unfilled arrow)307,

308, 318, 319

241 240, 320

Pyrene

Acylation238

Nitration235, 311

Halogenation67, 214

Oxidation with osmium tetroxide (unfilled arrow)321

Reaction with ethyl diazoacetate (unfilled arrow)240

‘Cyclohexatrine’

Epoxidation and hydrogenation {#1240}57, 59


S29

Figure S15. HOMOs and HOMO–1 orbitals and energies for theoretically challenging aromatic

molecules calculated using DFT/B3LYP/6-311G*. The locations of the largest HOMO lobes indicate that

the Frontier Molecular Orbital approximation for predicting nucleophilicity fails in many situations.


S30

Figure S16. Correlations of experimental nucleophilicity parameters, N with average local ionisation

energy minima ĪS,min calculated using the methods indicated at the 0.002 electrons/bohr3

surface (Table

S3).


S31

Figure S17. Correlations of experimental reactivity parameters with average local ionisation energies

calculated using HF/6-311G* at the 0.002 electrons/bohr3

surface: (a), Average local ionisation energies

taken over the meta and para positions vs. the corresponding Hammett substituent constants. (b),

Nucleophilicity parameters determined by Mayr and co-workers. (c), Experimental partial rate factors

for a range of electrophilic substitution reactions at different carbon positions in substituted benzenes.

(d), A scale of average local ionisation energies including representative examples. Tables S1-S3

contain the associated data and references. The main text contains a version of this figure plotted using

DFT/B3LYP/6-311G* values.


S32

Figure S18. Correlation of experimental partial rate factors for (a) bromination, (b) chlorination, and

(c) nitration taken from individual experimental studies vs. average local ionisation minima taken over

each reactive position calculated using DFT/B3LYP/6-311G* at the 0.002 electrons/bohr3

surface. Table

S2 contains the associated data and references.


S33

∑

∑ ( )

Figure S19. Correlation of experimental percentage yields (from Figure 4) and those derived from

partial rate factors for a range of electrophilic aromatic substitution reactions (y-axis) vs. those predicted

using the equation given above (x-axis). nj is the number of equivalent aromatic positions j that are

available for substitution, fj is the experimental partial rate factor at each position j (Table S2), m is the

gradient of the graph determined in Figure 3c (m = –21.194), and ĪS,j is the average local ionisation

energy taken over each position j (calculated using B3LYP/6-311G* at the 0.002 electrons/bohr3

surface). Figure 4 in the main text and Table S2 contain the associated data and references. In general,

yields can be predicted with ±25% accuracy. The outliers marked with hollow circles correspond to

examples where steric effects have an important influence on the observed product ratios (iodobenzene

and some polymethylbenzenes), which are not taken into account in the ionisation energy model.


S34

Table S1. Hammett m and p substituent constants and corresponding calculated average local ionisation

energy values ĪS meta and ĪS para taken directly over the centre of the carbons in the meta and para positions

when viewed perpendicular to the plane of the ring (as shown in Figure S1). a Entry numbers refer to

Table I of reference 26

.

DFT/B3LYP/6-311G* HF/B3LYP/6-311G*

Entrya Substituent m p ĪS meta /eV ĪS para /eV ĪS meta /eV ĪS para /eV

2 Br 0.39 0.23 9.69 9.61 12.63 12.56

5 Cl 0.37 0.23 9.71 9.60 12.64 12.53

7 SO2Cl 1.20 1.11 10.42 10.54 13.24 13.51

15 F 0.34 0.06 9.62 9.41 12.61 12.30

18 SO2F 0.80 0.91 10.38 10.50 13.24 13.52

28 I 0.35 0.18 9.71 9.66 12.62 12.60

31 NO 0.62 0.91 9.98 10.14 12.74 12.93

32 NO2 0.71 0.78 10.13 10.24 13.02 13.26

37 N3 0.37 0.08 9.42 9.41 12.53 12.13

43 H 0.00 0.00 9.25 9.25 12.13 12.13

45 OH 0.12 –0.37 9.32 8.96 12.39 11.84

49 SH 0.25 0.15 9.49 9.27 12.46 12.19

50 B(OH)2 –0.01 0.12 9.31 9.43 12.17 12.34

51 NH2 –0.16 –0.66 9.09 8.62 12.20 11.58

52 NHOH –0.04 –0.34 9.18 8.87 12.21 11.76

53 SO2NH2 0.53 0.60 9.88 9.96 12.76 12.97

59 NHNH2 –0.02 –0.55 9.21 8.76 12.33 11.68

60 SiH3 0.05 0.10 9.43 9.48 12.27 12.37

61 CBr3 0.28 0.29 9.79 9.83 12.65 12.71

62 CClF2 0.42 0.46 9.87 9.91 12.72 12.82

66 CCl3 0.40 0.46 9.86 9.92 12.69 12.79

70 CF3 0.43 0.54 9.83 9.90 12.70 12.83

75 OCF3 0.38 0.35 9.81 9.74 12.73 12.64

76 SOCF3 0.63 0.69 9.99 10.08 12.95 13.11

78 SO2CF3 0.83 0.96 10.33 10.45 13.21 13.53

80 OSO2CF3 0.56 0.53 9.96 9.91 13.01 12.98

81 SCF3 0.40 0.50 9.83 9.94 12.67 12.86

84 CN 0.56 0.66 10.06 10.10 12.94 13.05

85 NC 0.48 0.49 9.98 9.90 12.83 12.72

89 N=C=O 0.27 0.19 9.69 9.50 12.65 12.40

90 OCN 0.67 0.54 10.05 9.87 13.04 12.78

91 SO2CN 1.10 1.26 10.51 10.64 13.38 13.67

92 N=C=S 0.48 0.38 9.87 9.71 12.98 12.81

93 SCN 0.51 0.52 10.04 10.09 12.89 13.04

94 SeCN 0.61 0.66 10.00 10.08 12.86 13.00

97 C(NO2)3 0.72 0.82 10.44 10.52 13.39 13.63

102 OCHCl2 0.38 0.26 9.89 9.79 12.75 12.61


S35

103 CHF2 0.29 0.32 9.61 9.64 12.52 12.56

104 OCHF2 0.31 0.18 9.72 9.51 12.67 12.54

105 SOCHF2 0.54 0.58 9.95 9.99 12.89 13.03

106 SO2CHF2 0.75 0.86 10.16 10.31 13.03 13.35

107 SCHF2 0.33 0.37 9.78 9.82 12.66 12.78

109 NHSO2CF3 0.44 0.39 9.82 9.69 12.80 12.83

111 NHCN 0.21 0.06 9.72 9.40 12.76 12.28

117 CHO 0.35 0.42 9.78 9.89 12.58 12.75

118 COOH 0.37 0.45 9.63 9.78 12.47 12.71

119 CH2Br 0.12 0.14 9.57 9.56 12.43 12.41

120 CH2Cl 0.11 0.12 9.58 9.58 12.44 12.43

121 OCH2Cl 0.25 0.08 9.56 9.28 12.61 12.17

122 CH2F 0.12 0.11 9.37 9.32 12.34 12.23

123 OCH2F 0.20 0.02 9.52 9.21 12.56 12.12

124 SCH2F 0.23 0.20 9.73 9.78 12.59 12.70

125 CH2I 0.10 0.11 9.59 9.58 12.45 12.40

126 NHCHO 0.19 0.00 9.41 9.21 12.40 12.01

127 CONH2 0.28 0.36 9.58 9.65 12.42 12.60

133 Me –0.07 –0.17 9.19 9.11 12.09 11.96

139 NHCONH2 –0.03 –0.24 9.25 8.98 12.25 11.84

142 OMe 0.12 –0.27 9.24 8.91 12.28 11.79

143 CH2OH 0.00 0.00 9.52 9.52 12.40 12.40

144 SOMe 0.52 0.49 9.72 9.73 12.64 12.70

147 S(O)OMe 0.50 0.54 9.70 9.76 12.56 12.75

148 SO2Me 0.60 0.72 10.01 10.10 12.89 13.10

150 OSO2Me 0.39 0.36 9.57 9.37 12.69 12.39

151 SMe 0.15 0.00 9.49 9.51 12.29 12.37

152 SSMe 0.22 0.13 9.61 9.62 12.49 12.56

154 NHMe –0.21 –0.70 9.04 8.57 12.16 11.48

155 CH2NH2 –0.03 –0.11 9.10 9.08 12.02 11.95

158 N(COF)2 0.58 0.57 10.00 10.05 12.93 12.98

160 COCF3 0.63 0.80 10.00 10.17 12.80 13.06

161 SCOCF3 0.48 0.46 9.87 9.95 12.72 12.85

162 OCOCF3 0.56 0.46 9.89 9.81 12.81 12.68

165 CF2CF3 0.47 0.52 9.86 9.94 12.74 12.90

166 OCF2CF3 0.48 0.28 9.78 9.61 12.80 12.50

167 SO2CF2CF3 0.92 1.08 10.33 10.49 13.21 13.55

169 N(CF3)2 0.40 0.53 9.91 9.95 12.77 12.89

175 C≡CH 0.21 0.23 9.56 9.50 12.43 12.41

176 OCF2CHFCl 0.35 0.28 9.77 9.69 12.68 12.58

177 NHCOCF3 0.30 0.12 9.69 9.52 12.70 12.33

179 OCF2CHF2 0.34 0.25 9.66 9.48 12.66 12.36

180 SCF2CHF2 0.38 0.47 9.74 9.82 12.59 12.76

185 CH2CF3 0.12 0.09 9.51 9.50 12.41 12.42


S36

186 CH2SOCF3 0.25 0.24 9.65 9.66 12.56 12.59

187 CH2SO2CF3 0.29 0.31 9.77 9.80 12.66 12.74

188 CH2SCF3 0.12 0.15 9.45 9.50 12.41 12.38

189 CH2CN 0.16 0.18 9.67 9.65 12.58 12.55

193 CH=CH2 0.06 –0.04 9.34 9.26 12.23 12.11

198 oxiranyl 0.05 0.03 9.36 9.30 12.23 12.17

199 OCH=CH2 0.21 –0.09 9.46 9.14 12.47 12.01

200 COMe 0.38 0.50 9.61 9.74 12.46 12.61

201 SCOMe 0.39 0.44 9.50 9.51 12.38 12.47

202 OCOMe 0.39 0.31 9.50 9.39 12.43 12.25

203 COOMe 0.37 0.45 9.55 9.66 12.37 12.61

205 SCH=CH2 0.26 0.20 9.53 9.39 12.38 12.41

210 NHCOOMe –0.02 –0.17 9.32 9.03 12.30 11.89

211 NHCOMe 0.21 0.00 9.30 9.09 12.25 11.89

212 CONHMe 0.35 0.36 9.50 9.57 12.44 12.54

214 CH2CONH2 0.06 0.07 9.59 9.54 12.54 12.47

219 Et –0.07 –0.15 9.20 9.12 12.11 11.97

221 OCH2CH3 0.10 –0.24 9.21 8.88 12.27 11.80

222 CH(OH)Me 0.08 –0.07 9.34 9.29 12.21 12.14

223 CH2OMe 0.08 0.01 9.30 9.25 12.17 12.13

224 SO2Et 0.66 0.77 9.98 10.08 12.85 13.08

225 SEt 0.18 0.03 9.48 9.50 12.34 12.43

230 NHEt –0.24 –0.61 9.03 8.55 12.13 11.50

231 N(Me)2 –0.16 –0.83 8.99 8.54 12.10 11.43

236 N=NNMe2 –0.05 –0.03 9.13 8.96 12.13 11.96

239 PO(OMe)2 0.42 0.53 9.60 9.73 12.44 12.65

250 C≡CF3 0.41 0.51 9.94 9.95 12.80 12.83

251 CF=CFCF3–t 0.39 0.46 9.88 9.89 12.73 12.84

253 CF2CF2CF3 0.44 0.48 9.88 9.97 12.75 12.92

254 CF(CF3)2 0.37 0.53 9.85 9.91 12.75 12.88

255 SO2CF2CF3 0.92 1.09 10.33 10.48 13.21 13.57

256 SO2CF(CF3)2 0.92 1.10 10.33 10.48 13.19 13.55

257 SCF2CF2CF3 0.45 0.48 9.87 9.94 12.72 12.90

258 SCF(CF3)2 0.48 0.51 9.88 9.95 12.70 12.89

262 CH(CN)2 0.53 0.52 9.99 9.99 12.91 12.92

263 CHC=HCF3–c 0.16 0.17 9.61 9.63 12.43 12.43

264 CH=HCF3–t 0.24 0.27 9.74 9.71 12.59 12.55

266 CH=HCN–t 0.24 0.17 9.91 9.90 12.77 12.75

267 C=CMe 0.21 0.03 9.25 9.13 12.14 11.97

268 N(Me)COCF3 0.41 0.39 9.81 9.82 12.68 12.72

269 CH=CHCHO 0.24 0.13 9.80 9.80 12.62 12.60

270 cyclopropyl –0.07 –0.21 9.20 9.16 12.07 12.02

272 CH=CHCH3 0.02 –0.09 9.26 9.14 12.14 11.98

276 COEt 0.38 0.48 9.53 9.65 12.35 12.59


S37

277 COOEt 0.37 0.45 9.60 9.71 12.42 12.60

278 CH2OCOMe 0.04 0.05 9.46 9.47 12.34 12.30

288 isopropyl –0.04 –0.15 9.18 9.12 12.06 11.95

294 OCH2CH2CH3 0.10 –0.25 9.20 8.87 12.29 11.76

307 SiMe3 –0.04 –0.07 9.24 9.28 12.10 12.17

317 C(CF3)3 0.55 0.55 9.85 9.94 12.76 12.94

346 COCHMe2 0.38 0.47 9.61 9.72 12.41 12.60

348 NHCOCH(Me)2 0.11 –0.10 9.35 9.09 12.30 11.91

352 (CH2)3CH3 –0.08 –0.16 9.18 9.11 12.09 11.96

360 N(Et)2 –0.23 –0.72 8.96 8.44 12.09 11.31

434 N(C3H7)2 –0.26 –0.93 8.97 8.47 12.07 11.36

504 N(C6H5)2 0.00 –0.22 9.31 9.10 12.23 11.93

527 Si(C6H5)3 –0.03 0.10 9.25 9.33 12.08 12.21

529 C(C6H5)3 –0.01 0.02 9.20 9.18 12.10 12.07


S38

Table S2. Experimental partial rate factors for electrophilic substitution in different positions of

aromatic substrates and their corresponding average local ionisation energies, ĪS, j. Average local

ionisation energies were calculated using the methods indicated at the 0.002 electrons/bohr3 surface (as

shown in Figure S1). % yields were calculated from DFT ionisation energies using the equations given

in Figure S19. Predicted % yields are and are associated with an error of up to ±25% (Figure S19).

Experimental partial rate factors are taken from references21,44, 74, 322, 323.

Ave. Local Ionisation

Energy, ĪS,j /eV (predicted % yields)

ln (experimental partial rate factor), ln(fj) (corresponding % yields where all partial rates known)

Compound

Po

sit

ion

, j

DF

T/B

3LY

P

6-3

11

G*

HF

/

6-3

11

G*

Bro

min

atio

n

Ch

lori

na

tio

n

Nitra

tio

n

Be

nzyla

tio

n

So

lvo

lysis

Eth

yla

tio

n

Me

rcu

ratio

n

Ace

tyla

tio

n

Benzene 1 9.25 (100%) 12.12 0.0 (100%) 0.0 (100%) 0.0 (100%) 0.0 (100%) 0.0 0.0 0.0 0.0

Toluene 2 9.07 (70%) 11.94 6.40 (68%) 6.40 (60%) - - - - - -

3 9.18 (7%) 12.10 1.70 (1%) 1.59 (0%) 0.74 - 0.67 0.39 0.81 1.57

4 9.09 (23%) 11.98 7.78 (31%) 6.70 (40%) 3.89 - 3.21 1.75 3.15 6.61

1,2-dimethylbenzene 3 9.02 (60%) 11.91 8.06 (20%) 7.9 (43%) - - - - - -

4 9.04 (40%) 11.94 9.44 (80%) 8.2 (57%) - - - - - -

1,3-dimethylbenzene 2 8.91 (48%) 11.78 12.66 12.6 - - - - - -

4 8.94 (51%) 11.78 14.05 12.9 - - - - - -

5 9.13 (0%) 12.07 - - - - - - - -

1,4-dimethylbenzene 2 9.03 (100%) 11.92 8.29 (100%) 8.0 (100%) - - - - - -

1,2,3-trimethylbenzene 4 8.88 (95%) 11.76 15.43 (100%) - - - - - - -

5 8.99 (5%) 11.91 10.82 (0%) - - - - - - -

1,2,4-trimethylbenzene 3 8.86 (52%) 11.76 14.51 (20%) - - - - - - -

5 8.87 (42%) 11.75 15.89 (80%) - - - - - - -

6 8.97 (5%) 11.88 9.67 (0%) - - - - - - -

1,3,5-trimethylbenezene 2 8.77 (100%) 11.60 19.8 (100%) 17.9 (100%) - - - - - -

1,2,3,4-tetramethylbenzene 5 8.83 (100%) 11.72 17.27(100%) - - - - - - -

1,2,3,5-tetramethylbenzene 4 8.73 (100%) 11.60 20.95 (100%) - - - - - - -

1,2,4,5-tetramethylbenzene 3 8.82 (100%) 11.73 15.89 (100%) 15.4 (100%) - - - - - -

Pentamethylbenzene 6 8.67 (100%) 11.53 22.34 (100%) 20.5 (100%) - - - - - -

Nitrobenzene 2 10.31 (3%) 13.41 - - -18.3 (6%) - - - - -

3 10.14 (92%) 13.03 - - –15.6 (92%) - - - - -

4 10.24 (6%) 13.26 - - –18.7 (2%) - - - - -

t-Butylbenzene 2 9.08 (66%) 11.91 - - - - - - - -

3 9.16 (17%) 12.03 1.80 1.68 1.34 - 0.62 - 1.22 2.56

4 9.12 (17%) 11.95 6.70 5.99 4.05 - 2.67 - 2.86 6.49

Chlorobenzene 2 9.66 (28%) 12.66 - - - –1.4 (33%) - - - -

3 9.71 (10%) 12.65 –7.09 –8.11 –7.09 –5.4 (1%) –

4.17 –4.17 –2.28 –7.48

4 9.59 (62%) 12.53 –1.93 –0.97 –2.05 0.0 (67%) –

1.20 –0.62 –1.01 –2.07

Bromobenzene 2 9.65 (31%) 12.70 - - - –1.7 (33%) - - - -

3 9.69 (13%) 12.64 –6.93 –1.24 –6.90 –5.6 (1%) –

4.17 -4.24 –2.44 –7.55


S39

4 9.59 (56%) 12.56 - 1.47 –2.30 –0.3 (67%) –

1.57 –1.57 - -

Fluorobenzene 2 9.47 (23%) 12.47 –2.79 - - –1.6 (14%) - - - -

3 9.60 (1%) 12.61 1.52 - –2.28 –5.9 (0%) –

3.68 –0.83 –1.31 –2.49

4 9.38 (76%) 12.31 - - –0.25 0.9 (86%) 0.76 –0.30 1.08 0.41

Iodobenzene 2 9.71 (26%) 12.73 - - - –1.4 (31%) - - - -

3 9.71 (26%) 12.64 - - - –5.1 (1%) - - - -

4 9.65 (47%) 12.60 - - - 0.1 (69%) - - - -


S40

Table S3.Experimental nucleophilicity parameters, N and corresponding average local ionisation energy

minima ĪS,min taken nearest to the carbons marked with arrows. Average local ionisation energies were

calculated with the methods indicated and taken at the 0.002 electrons/bohr3 surface. This data is plotted

graphically in Figures 3, S16 and S17. a n.s. denotes entries with atoms not supported by a particular basis

set.

Structure

Nu

cle

op

hilic

ity

pa

ram

ete

r, N

So

lven

t

DF

T/B

3L

YP

/ 6-3

1G

*

DF

T/B

3L

YP

/ 6-3

1G

**

DF

T/B

3L

YP

/ 6-3

1+

G*

DF

T/B

3L

YP

/

6-3

11G

*

DF

T/B

3L

YP

/ 6-3

11+

G**

DF

T/B

3L

YP

/

6-3

11+

+G

**

DF

T/B

3L

YP

/ L

AC

VP

HF

/6-3

1G

*

HF

/6-3

11G

*

Refe

ren

ce

–4.47 DCM 9.02 9.06 9.01 9.07 8.98 8.97 9.02 11.94 11.94 324

–3.54 DCM 8.86 8.88 8.82 8.92 8.78 8.77 8.84 11.76 11.75 324

2.48 DCM 8.55 8.57 8.58 8.55 8.53 8.53 8.63 11.47 11.42 324

0.13 DCM 8.71 8.73 8.68 8.72 8.64 8.64 8.75 11.59 11.57 324

6.66 ACN 8.34 8.37 8.32 8.38 8.29 8.28 8.28 10.93 10.93 325

–1.18 DCM 8.86 8.89 8.87 8.88 8.83 8.82 8.91 11.78 11.75 326

1.26 DCM 8.71 8.73 8.65 8.77 8.60 8.59 8.74 11.81 11.83

324

3.61 DCM 8.36 8.39 8.37 8.44 8.38 8.38 8.52 11.30 11.32

324

5.85 DCM 7.83 7.87 7.87 7.89 7.86 7.86 7.80 10.74 10.72 324

1.36 DCM 8.55 8.59 8.61 8.65 8.64 8.63 8.76 11.48 11.52

324

10.67 ACN 7.68 7.70 7.65 7.68 7.63 7.63 7.61 10.57 10.50 325


S41

8.69 ACN 7.66 7.68 7.60 7.70 7.59 7.59 7.60 10.53 10.52 325

8.01 ACN 7.67 7.70 7.60 7.71 7.67 7.66 7.63 10.57 10.55 325

11.63 ACN 7.68 7.70 7.60 7.68 7.59 7.60 7.60 10.56 10.48 325

6.22 DCM 8.05 8.08 8.05 8.07 8.05 8.05 8.04 10.97 10.95 327

5.55 DCM 8.14 8.18 8.15 8.18 8.16 8.16 8.10 11.01 11.00 327

5.75 DCM 8.12 8.15 8.14 8.16 8.07 8.07 8.05 10.98 10.97 327

2.16 DCM 8.33 8.35 8.47 8.48 8.51 8.50 8.44 11.16 11.24

326

3.97 ACN 8.50 8.53 8.47 8.53 8.53 8.53 8.50 11.36 11.33 327

7.26 ACN 7.93 7.95 7.91 7.96 7.89 7.89 7.90 10.82 10.82 327

7.22 ACN 7.91 7.93 7.89 7.95 7.88 7.89 7.85 10.78 10.79 327

6.91 ACN 7.97 7.99 7.96 8.01 7.97 7.96 7.91 10.83 10.84 327

6.08 ACN 8.30 8.30 8.27 8.35 8.25 8.25 8.31 11.18 11.19 327

5.41 ACN 8.00 8.04 8.02 8.03 8.03 8.02 7.96 10.87 10.84 327


S42

3.87 ACN 8.37 8.41 8.38 8.41 8.39 8.39 8.40 11.23 11.21 327

2.83 ACN 8.76 8.80 8.76 8.80 8.78 8.78 8.71 11.63 11.62 327

4.38 ACN 8.44 8.46 8.44 8.49 8.44 8.44 8.46 11.36 11.33 327

4.42 ACN 8.44 8.47 8.42 8.48 8.42 8.42 8.46 11.33 11.32 327

2.20 DCM 8.36 8.38 8.52 8.50 8.52 8.51 8.45 11.20 11.25

326

2.37 DCM 8.40 8.42 8.51 8.49 8.53 8.52 8.53 11.21 11.25

326

–1.01 DCM 8.86 8.89 8.83 8.92 8.80 8.79 8.92 11.97 12.00

326

–0.80 DCM 8.65 8.67 8.72 8.79 8.75 8.74 8.88 11.65 11.70

326

3.63 DCM

an.s. n.s. n.s. n.s. n.s. 8.62 n.s. n.s. n.s.

326

1.53 DCM n.s. n.s. n.s. n.s. n.s. 8.85 n.s. n.s. n.s.

326

4.63 DCM 7.88 7.93 7.97 7.93 7.98 7.98 7.88 10.81 10.77

328

6.54 DCM 7.95 7.97 7.90 8.00 7.88 7.88 7.87 10.80 10.82 327

6.44 ACN 8.10 8.14 8.13 8.14 8.14 8.13 8.13 11.04 11.02 327

6.00 ACN 8.08 8.12 8.07 8.12 8.07 8.08 8.04 10.97 10.96 327

7.22 ACN 7.95 7.97 7.96 7.96 7.97 7.97 7.80 10.90 10.88 327


S43

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